Abstract In traditional thermodynamics it is assumed that isentropic, reversible, adiabatic processes can be summoned up on demand and straightforwardly accomplished. By contrast, taking entropy as the maximised uncertainty of a final equilibrium state of a quantised system, it is not obvious that an associated process can always be found that is both rigorously isentropic and reversibly adiabatic. In fact, we find that linear relations between generalized forces X j (such as pressures P j ) and energies E j are necessary and sufficient conditions for a reversible quasi-static and adiabatic change to be truly isentropic. However, such relationships only hold for a few especially simple systems, such as the perfect gas and the idealised paramagnet. They do not generally hold to all orders for more complicated systems. By considering the associated entropy increases up to second order in small changes of the conjugate displacements (such as the volume V j ) we argue that the consequences are nevertheless in practice negligible.
Abstract In traditional thermodynamics it is assumed that isentropic, reversible, adiabatic processes can be summoned up on demand and straightforwardly accomplished. By contrast, taking entropy as the maximised uncertainty of a final equilibrium state of a quantised system, it is not obvious that an associated process can always be found that is both rigorously isentropic and reversibly adiabatic. In fact, we find that linear relations between generalized forces X j (such as pressures P j ) and energies E j are necessary and sufficient conditions for a reversible quasi-static and adiabatic change to be truly isentropic. However, such relationships only hold for a few especially simple systems, such as the perfect gas and the idealised paramagnet. They do not generally hold to all orders for more complicated systems. By considering the associated entropy increases up to second order in small changes of the conjugate displacements (such as the volume V j ) we argue that the consequences are nevertheless in practice negligible.
We examine the fundamental aspects of statistical mechanics, dividing the problem into a discussion purely about probability, which we analyse from a Bayesian standpoint. We argue that the existence of a unique maximising probability distribution {p(j∣K)} for states labelled by j given data K implies that the corresponding maximal value of the information entropy σ({(pj∣K)})=−∑j(pj∣K)ln(pj∣K) depends explicitly on the data at equilibrium and on the Hamiltonian of the system. As such, it is a direct measure of our uncertainty about the exact state of the body and can be identified with the traditional thermodynamic entropy. We consider the well known microcanonical, canonical and grand canonical methods and ensure that the fluctuations about mean values are generally minuscule for macroscopic systems before identifying these mean values with experimental observables and thereby connecting to many standard results from thermodynamics. Unexpectedly, we find that it is not generally possible for a quantum process to be both isentropic and reversibly adiabatic. This is in sharp contrast to traditional thermodynamics where it is assumed that isentropic, reversible adiabatic processes can be summoned up on demand and easily realised. By contrast, we find that linear relations between pressures Pj and energies Ej are necessary and sufficient conditions for a quasi-static and adiabatic change to be isentropic, but, of course, this relationship only holds for a few especially simple systems, such as the perfect gas, and is not generally true for more complicated systems. By considering the associated entropy increases up to second order in small volume changes we argue that the consequences are in practice negligible.
Abstract The quantum thermodynamics of the ideal gas is treated by means of the particle entropies σ=ka. The non-dimensional entropy numbers a are calculated by the extended, temperature-dependent Schrödinger equation applying periodic boundary conditions. The Boltzmann constant k represents the atomic entropy unit. The quantized particle entropies a are used to calculate the Boltzmann distribution f=exp(α−a), the density of entropy levels D(a), the dimensionless chemical potential α=μ/kT, etc. – The thermodynamics of the ideal gas is treated on the basis of entropy quanta by means of the density matrix formalism. In this way we obtain the total particle entropy A, the thermodynamic entropy S (equation of Sackur-Tetrode), the internal and the Helmholtz free energy E and F, respectively, etc. Moreover, it can also be shown on the basis of entropy quanta that the entropy of a closed system in thermal equilibrium has a maximum value, S=S max. Against this, the entropy S ′ of an arbitrary non-equilibrium state is always smaller, S′ < S max (second law of thermodynamics). – Application of ordinary density matrix theory to a closed system of N particles leads to the result that the entropy S does not change in time, dS/dt=0, regardless whether we consider an equilibrium state, S=S max, or a non-equilibrium state, S=S′. Consequently, S cannot irreversibly change from S′ to S max. However, any irreversible process is accompanied by a positive entropy production P=dS/dt>0. In order to overcome this obvious contradiction, we discuss the entropy evolution in time by means of the commutator equation G =i[ P , t ], which is deduced from very general assumptions. Here P and t are the operators of the entropy production P and the time t. Accordingly, P and t do not commute in general, and hence P and t are not sharply defined simultaneously. Instead we have uncertainties ΔP and Δt, which are expressed by the uncertainty relation of the N-particle system, ΔPΔt≥(1/2)|〈 G 〉|=(γ/2)k. This P − t uncertainty relation easily allows a discussion of the evolution of the entropy S in time t from S′ to S max. Now the irreversible steps are correctly described by the entropy production P=dS/dt > 0, and the thermal equilibrium by P=0, ∆P=0, and thus the lifetime ∆t=∞.
Abstract In this paper the thermodynamical properties of any system whatsoever are deduced from quantum mechanics. Two fundamental irreversible processes are considered: the conversion of other forms of energy into heat, and the flow of heat from one temperature to another. By the proof of a generalized H -theorem, it is shown that in each case the entropy, correctly defined, must increase, and the system tend towards a state of equilibrium. A simple but rigorous proof of Boltzmann’s law is given from which the thermodynamics of reversible processes may be inferred. An appendix includes the exact solution of the most general time-dependent perturbation problem of quantum mechanics.
Abstract We consider the temporal evolution of an isolated system of N particles from a non-equilibrium state of entropy S = S′ to the equilibrium state of maximum entropy, S = S max, S′ ≤ S max. The application of usual density matrix theory to the temporal development of S leads us to dS/dt = 0: The entropy S does not change in time t. Thereby it is irrelevant, whether we consider a non-equilibrium state or an equilibrium state. Consequently, the system cannot irreversibly change by entropy production dS/dt > 0 from S′ to S max. This is a paradoxial result, which contradicts the experience. It can be traced back to the von Neumann equation, which in principle describes reversible processes and hence is unsuitable for calculating the irreversible evolution of the entropy S in time t. Each irreversible process is accompanied by a positive entropy production P = dS/dt ≥ 0 inside the system, which only vanishes in case of the equilibrium state. In order to overcome the above mentioned difficulties, we assign an operator P to the entropy production P, which is defined by the eigenvalue equation P |u〉 = P|u〉 with the state vector |u〉 of the N-particle system. There was an extensive discussion about the relation between the production of entropy P on one hand and the progression of time t on the other. Making use of this concept, we combine the operator of entropy production P with the time-development operator U (t, t 0) of the system and finally deduce the infinitesimal unitary operator U (t+τ,t) = 1 + (i/k)τ P by means of very general assumptions. Here P means the generator of the infinitesimal progression of time τ = t − t 0 and k the Boltzmann constant, representing the atomic entropy unit. Similarly to P we also treat the time t as an observable, defined by t |u〉 = t|u〉. We apply the infinitesimal time-evolution operator U (t+τ,t) to the operator of time t and finally obtain the P – t commutation relation i[ P , t ] = k, which is independent of τ. It shows that the operators P and t do not commute, and hence P and t are not sharply defined simultaneously. Instead we have uncertainties ΔP and Δt on measuring P and t, which are given by the P–t uncertainty relation ΔPΔt ≥ k/2. It readily allows a discussion of the evolution of the entropy S of the isolated system in time t from S′ to S max. Now, the irreversible steps are correctly described by the entropy production P = dS/dt > 0, while the thermal equilibrium is given by P = 0, ΔP = 0, and thus the lifetime of the equilibrium state Δt = ∞. According to the P–t uncertainty relation, the Boltzmann constant k is similarly important to the quantum thermodynamics of irreversible processes like Planck′s constant h to usual quantum mechanics.
Abstract Quantum thermodynamics describes dynamic processes by means of the operators of entropy production P and time t . P and t do not commute. It exists the non-vanishing t–P commutator [ t , P ]=ik. Here the Boltzmann constant k has the physical meaning of a quantum of entropy. The t–P commutator immediately leads us to the t–P uncertainty relation ΔtΔP≥k/2. Hence the observables t and P are not sharply defined simultaneously. Similar uncertainty relations can also be expected for other pairs of conjugate variables with products of the physical meaning of an entropy. The free energy F and the reciprocal temperature (1/T) are the respective conjugate variables of an isolated system of many particles, which leads us to the F–(1/T) uncertainty relation ǀΔFǁΔ(1/T)ǀ≥k/2. It can be traced back to the t–P uncertainty relation mentioned above. In this way the Helmholtz free energy F and the temperatur T are introduced into quantum thermodynamics. The uncertainties ǀΔFǀ→0 and ǀΔTǀ→0 are negligible at low temperatures T→0, and quantum thermodynamics turns into the time-independent classical thermodynamics. Against this the uncertainties ǀΔFǀ→∞ and ǀΔTǀ→∞ grow unlimited at high temperatures T→∞, and classical thermodynamics loses its sense. In the limit of one particle the uncertainties cannot be neglected even at low temperatures. However a detailed discussion shows that the free energy f of a single particle vanishes within the whole range of temperatures T. This defines the particle entropy σ=ε/T=ak. The dimensionless entropy number a connects the particle energy ε=akT with the temperature T. The entropy number a of a single (s) independent particle can be calculated with the extended, temperature-dependent Schrödinger equation A s φ=aφ. Here A s=−(Λ 2/4π)∇2 means the dimensionless entropy operator describing the entropy number a and thus the particle entropy σ=ak. Λ is the thermal de Broglie wave length. Finally we calculate by means of quantized particle entropies σ the internal energy E, the Helmholtz free energy F, the entropy S, the chemical potential μ, and the equation of state of an ideal gas of N monatomic free particles in full agreement with classical thermodynamics. We also calculate the partition function q=V/Λ 3 of a single free particle within the volume V. Here Λ 3 is a small volume element taking into account the wave–particle dualism of a single free particle of mass m at temperature T. Extension to a system of N free particles leads us to a simple geometrical model and to the conclusion that an ideal gas of independent particles becomes instable below a critical temperature T C. T C corresponds to the critical temperature T BE of Bose–Einstein condensation.
We consider the temporal evolution of an isolated system of particles from a non-equilibrium state of entropy S = S′ to the equilibrium state of maximum entropy S = S max, S′ ≤ S max. The application of usual density matrix theory to the temporal development of S leads us to the unexpected result P = dS/dt = 0. The entropy does not change in time. This result is valid in case of the equilibrium state. However it is wrong for a non-equilibrium state, which could not irreversibly change from S′ to S max by entropy production P > 0. This contradicts the second law of thermodynamics. The paradoxial result can be traced back to the Liouville theorem. To overcome this difficulty, we introduce the t–P space. The time t and the entropy production P are observables in quantum thermodynamics. They are defined by the eigenvalue equations t|t〉 = t|t〉 and P|P〉 = P|P〉. The operators t and P do not commute. We have a non-vanishing commutator, [t,P] = ik, and consequently a t–P uncertainty relation, ΔtΔP ≥ k/2. The Boltzmann constant k is characteristic of quantum thermodynamics and represents the atomic entropy unit. — The time evolution operator U(τ) = exp[−(i/k)τP] shifts the time t by τ, U(τ)|t〉 = |t + τ〉. The generator of τ is the operator P of entropy production. Then the eigenvector |P〉 is also an eigenket of U(t), and it follows with progressing time τ ≥ 0 that τP ≥ 0 and hence P = dS/dt ≥ 0. This is the second law of thermodynamics, which is correctly reproduced in quantum thermodynamics. — Exchanging −τ for +τ replaces the equations of forward time +τ by the equations of backward time −τ. Independent of the direction of the arrow of time, the entropy of the system always increases or remains constant in the limit of the equilibrium state, dS ≥ 0. This is characteristic of irreversibility, for the system does not return to its initial state on time reversal. — The t–P uncertainty relation allows to discuss the temporal evolution of the expectation value 〈P〉 of entropy production and the lifetime Δt of the transient states, the system passes through on approaching the equilibrium state. In case of a non-equilibrium state 〈P〉, ΔP, and Δt are finite. On approaching the equilibrium state, 〈P〉 and ΔP decrease, consequently Δt increases. Finally, in the case of equilibrium (eq), we have 〈P〉eq = 0, ΔP eq = 0, and Δt eq → ∞. The lifetime of the equilibrium state is unlimited, because the entropy production 〈P〉 and the uncertainty of entropy production ΔP exactly vanish. The temporal evolution of the system can be described by means of a phenomenological equation.